Well-structured bimetallic surface capable of molecular recognition for chemoselective nitroarene hydrogenation

Chemical Science
Shinya FurukawaTakayuki Komatsu

Abstract

Unprecedented molecular recognition ability governed by a simple bimetallic surface is reported. A series of Rh-based ordered alloys supported on silica gel (Rh x M y /SiO2, where M is Bi, Fe, Ga, Ge, In, Ni, Pb, Sb, Sn, or Zn) were tested in the hydrogenation of nitrostyrene to form aminostyrene. RhIn/SiO2 showed remarkably high catalytic activity and good selectivity under 1 atm H2 at room temperature. Moreover, various other nitroarenes containing carbonyl, cyano, or halo moieties were selectively hydrogenated into the corresponding amino derivatives using RhIn/SiO2. Kinetic study and density functional theory (DFT) calculations revealed that the high selectivity originates from RhIn/SiO2 adsorbing nitro groups much more favorably than vinyl groups. In addition, the DFT calculations indicated that the RhIn ordered alloy presents concave Rh rows and convex In rows on its surface, which are able to capture the nitro group with end-on geometry while effectively minimizing vinyl-π adsorption. Thus, the specific and highly ordered surface structure of RhIn enables the chemoselective molecular recognition of nitro groups over vinyl groups through geometric and chemical effects.

References

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Citations

Sep 7, 2019·Science and Technology of Advanced Materials·Shinya FurukawaKen-Ichi Shimizu
Nov 2, 2017·Chemistry, an Asian Journal·Yongjian AiQionglin Liang
Feb 17, 2018·Advanced Materials·Hao FangQingsheng Wu
Feb 29, 2020·Chemical Science·Yifan SunRaymond E Schaak
Mar 8, 2017·Chemical Communications : Chem Comm·Masazumi TamuraKeiichi Tomishige
Mar 30, 2021·Inorganic Chemistry·Biplab KoleyPartha P Jana
Jan 10, 2017·ACS Applied Materials & Interfaces·Vijaykumar S MarakattiSebastian C Peter
Oct 2, 2019·ACS Applied Materials & Interfaces·Xiangru WeiZhangxiong Wu
Nov 29, 2017·Journal of the American Chemical Society·Masayoshi MiyazakiTakayuki Komatsu
Nov 11, 2021·Physical Chemistry Chemical Physics : PCCP·Huaquan HuangWeidong Zhu
Jan 6, 2022·The Journal of Organic Chemistry·Mingyeong JangMin Su Han

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Methods Mentioned

BETA
X-ray
transmission electron microscopy

Software Mentioned

DMol
CASTEP

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